JP3326853B2 - Fluororesin aqueous dispersion and aqueous coating composition containing the aqueous dispersion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention provides a new and useful
The present invention relates to a fluororesin aqueous dispersion and an aqueous coating composition containing the same. More specifically, the present invention provides a specific, so-called reactive nonionic emulsifier, obtained by polymerizing with a fluoroolefin or the like, not only super-high weather resistance and stain resistance, but also,
The present invention relates to an aqueous fluororesin dispersion and an aqueous coating composition containing the same, each of which has excellent long-term storage stability.

[0002]

2. Description of the Related Art Conventionally, the purpose of coating surfaces of various kinds of alkaline inorganic cured products such as metals or cements and various kinds of plastics with a paint is to improve the weather resistance of the base material,
It is used for improving so-called durability such as chemical resistance and water resistance, and for protection and beauty.

[0003] In recent years, in particular, coating materials which are exposed to the outdoors such as building exterior materials and industrial materials are required to have excellent durability and to be maintenance-free for a long period of time.

[0004] Fluoroolefin-based copolymers are known as binders having high weather resistance and high chemical resistance, and are commercially available in the form of an organic solvent solution. However, since it contains a large amount of organic solvents, there are problems such as fire danger and harm and air pollution, and an aqueous fluoroolefin-based binder is required.

[0005] So far, tetrafluoroethylene,
Aqueous dispersions of various fluoroolefin polymers, such as vinylidene fluoride or hexafluoropropylene, have been proposed.

However, these fluoroolefins.
Polymer aqueous dispersions require baking at a high temperature during the film formation process. For example, in the invention described in JP-A-57-38845, vinylidene fluoride and In the case of a hexafluoropropylene copolymer, baking at a temperature of 180 to 230 ° C is required.

[0007] Such high-temperature baking is, of course, impossible in the field of ordinary dry paints (room temperature dry paints), in which paint is applied on site, and is what is called a factory where heating and drying are mainly performed. Even in line painting, it is undeniable that it is economically disadvantageous.

On the other hand, in the invention described in Japanese Patent Application Laid-Open No. 61-26167, as a solution to such a problem, fluoroolefin, alkyl vinyl ether,
An emulsion polymer-based coating composition comprising a vinyl carboxylate is disclosed. According to the invention, the film-forming properties are greatly improved.

The invention described in Japanese Patent Application Laid-Open No. 61-26167 discloses an emulsion copolymer-based coating resin composition comprising a fluoroolefin, an alkyl vinyl ether and a carboxylic acid vinyl ester. However, for applications such as the protection of inorganic building materials, they can be adapted, but they are not sufficient in terms of long-term storage stability and pigment dispersibility, and mechanical and chemical stability. It is something.

Further, according to the invention described in JP-A-2-225550, it is disclosed that an aqueous dispersion having good storage stability can be obtained by copolymerizing a macromonomer having a hydrophilic group. ing. However, the reality is that practical storage stability has not yet been obtained.

[0011]

As described above, as long as the conventional technology is followed, it is particularly excellent in long-term storage stability and, in addition, has both ultra-high weather resistance and excellent stain resistance. It is difficult and difficult to obtain a fluororesin aqueous dispersion (hereinafter, also referred to as an aqueous dispersion) in the form and an aqueous coating composition containing the fluororesin aqueous dispersion. I know that.

However, the present inventors have eagerly started research on the basis of the above-mentioned various drawbacks in the prior art and the above-mentioned various demands in the art.

Accordingly, an object of the present invention is to provide an aqueous fluororesin dispersion having excellent long-term storage stability, and an essential component comprising the aqueous dispersion and a pigment. It is to provide an aqueous coating composition.

[0014]

Means for Solving the Problems Accordingly, the present inventors have:
In light of the advantages or disadvantages of the prior art, as a result of diligent and repeated studies, a specific reactive emulsifier and fluoroolefin were emulsion-polymerized to make it an essential raw material component, and if necessary, other monomers. The present invention has now been completed by finding that a fluororesin aqueous dispersion obtained by emulsion-polymerizing these compounds can also satisfy the above-mentioned problems satisfactorily.

That is, the present invention relates to a nonionic emulsifier having at least one ethylenically unsaturated bond (hereinafter referred to as a nonionic emulsifier).
Abbreviated as reactive nonionic emulsifier. ), In the presence of a fluoroolefin as an essential component, a fluororesin aqueous dispersion obtained by emulsion polymerization of other monomers,
In addition, the aqueous dispersion is prepared by incorporating pigments,
An aqueous coating composition comprising an aqueous dispersion and, if necessary, a pigment, a thickener and / or an organic solvent. They try to provide things.

The above-mentioned reactive nonionic emulsifiers refer to a stable emulsified state at all stages of the polymerization reaction of the fluororesin aqueous dispersion of the present invention, that is, before, during or after the polymerization. It is for maintaining and not decomposing in an aqueous medium, without causing the ethylenically unsaturated double bond to inhibit the polymerization of monomers including fluoroolefins, and for causing random copolymerization, And emulsifiers that do not retain various reactive polar groups such as carboxylic acid groups, sulfonic acid groups or phosphoric acid groups.

When a so-called anionic or cationic reactive emulsifier having a reactive polar group is used alone, the stability of the aqueous dispersion tends to depend on the pH. This is inconvenient because it becomes a salt or forms a salt by neutralization, which adversely affects the properties of the coated film such as water resistance.

Even with nonionic emulsifiers, the dispersion particles themselves are fluoropolymers that form relatively low-energy particle surfaces, and therefore, compared to ordinary polymers such as acrylic emulsions. It has strong water or oil repellency and does not strongly adsorb emulsifiers.

Therefore, there is naturally a limit in adsorbing and stabilizing the emulsifier on the dispersion particles only by an intermolecular force or an electric force, and therefore, a force due to chemical bonding is absolutely necessary. It becomes.

For the above reasons, the reactive nonionic emulsifier is an essential component for improving the stability of the aqueous dispersion. If only typical representative examples of the reactive nonionic emulsifiers are given, the following general formula can be used.

[0021]

Embedded image

Wherein R ₁ and R ₂ may be the same or different and each have 6 carbon atoms.
And represents a hydrocarbon group having at least one, preferably one or two polymerizable unsaturated bonds, and R ₃ is an alkyl group having 1 to 4 carbon atoms. Alternatively, A represents a proton, A represents an ethylene oxide bond and / or a propylene oxide bond, m is an integer of 1 or 2, and n is an integer of 5 or more. ]

[0023]

Embedded image

Wherein R ₁ is a group having 6 to 2 carbon atoms.
4 becomes saturated or is to represent an unsaturated hydrocarbon group, R _2, if R ₁ is a saturated hydrocarbon group, a represents an alkenyl group having a carbon number becomes 2 to 4, R ₁
Is an unsaturated hydrocarbon group, A represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond, and m is an integer of 1 or 2. There is,
Further, n is an integer of 5 or more. ]

[0025]

Embedded image

Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ represents a hydrocarbon group having 1 to 4 carbon atoms. A represents an alkyl group or a proton, A represents an ethylene oxide bond and / or a propylene oxide bond, m is an integer of 1 or 2, and n is an integer of 5 or more. . ]

[0027]

Embedded image

Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ represents a proton or a methyl group. R ₃ represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond, and n is an integer of 5 or more. ]

[0029]

Embedded image

Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ represents a proton or a methyl group. R ₃ represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond, and n is an integer of 5 or more. ]

[0031]

Embedded image

Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ and R ₃ are the same as each other. May be different from each other.
4 represents an alkyl group or a proton;
And B each represent an ethylene oxide bond and / or a propylene oxide bond, which may be the same or different, and m and n may each be the same or different, At least one of them is an integer of 5 or more, and the other is an integer of 0 or 1 or more. ]

[0033]

Embedded image

Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ and R ₃ are the same as each other. May be different from each other.
4 represents an alkyl group or a proton;
And B represent an ethylene oxide bond and / or a propylene oxide bond, which may be the same or different, and m and n
May be the same or different,
At least one of them is an integer of 5 or more, and the other is an integer of 0 or 1 or more. ]

[0035]

Embedded image

Wherein R ₁ and R ₂ may be the same or different and each have 6 carbon atoms.
To 24, wherein at least one of them is an alkyl group, and A and B may be the same or different, and each may be an ethylene oxide bond and / or Or m represents a propylene oxide bond, and m and n may be the same or different, and at least one of them is an integer of 5 or more, and the other is 0 or 1. It is assumed that the integer is the above integer, and that r is an integer of 1 to 4. 〕and

[0037]

Embedded image R ₁ COO (A) _n R _{2 wherein} R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms; R ₂ represents an alkyl group having 1 to 4 carbon atoms or a proton, A represents an ethylene oxide bond and / or a propylene oxide bond, and m and n are the same or different. However, at least one of them is an integer of 5 or more, and the other is an integer of 0 or 1 or more. The hydrophilic segment is, via an ether bond, polymerizable via an ether bond, as long as it has a chemical structure represented by Of vinyl ether type linked to unsaturated double bonds, for example

[0038]

Embedded image CH ₂ ＣＨCHO (CH ₂ ) _m (OCH ₂ CH ₂ ) _n -OH
... [X] [wherein, m and n in the formula may be the same or different, and each is an integer of 1 or more; m is an integer of 1 to 20; It shall be an integer of 1 or more. And the like, when used in an aqueous medium, under certain conditions, can easily cause hydrolysis, so that the use of such compounds must be avoided.

In addition, other compounds, ie, for example,

[0040]

CH ₂ ＣＨCHCH ₂ O (CH ₂ ) _m (OCH ₂ CH ₂ ) _n —O
H ... [XI] [wherein, m and n in the formula may be the same or different, and each is an integer of 1 or more; m is an integer of 1 to 20, n is an integer of 1 or more. ] And the like,
If incorporated into polymer particles, it can exhibit its particle stabilizing ability, but it is necessary to avoid using it because it lacks the ability to sufficiently emulsify monomers before polymerization. .

Specific examples of the compound represented by the general formula [I] include (polyoxyethylene) ₂₀ nonyl (allylated) phenyl ether. This compound is obtained by adding nonylphenol to ethylene oxide and / or
Or addition polymerization of propylene oxide, and then
It can be obtained by substituting a hydrogen atom in the benzene nucleus of the alkylphenol with an allyl group. Specific compounds of the compound represented by the general formula [II] include:
Acryloylated (polyoxyethylene) ₃₀ nonylphenyl ether. This compound is obtained by subjecting nonylphenol to addition polymerization of ethylene oxide and / or propylene oxide, followed by an esterification reaction with a compound containing a carboxyl group-containing unsaturated double bond such as acrylic acid. General formula [III]
Specific examples of the compound represented by are (polyoxyethylene) ₃₀ octenyl phenyl ether. This compound can be obtained by addition polymerization of octenylphenol with ethylene oxide and / or propylene oxide. Specific examples of the compound represented by the general formula [IV] include (polyoxyethylene) ₃₀ -decadienecarboxylic acid acetic acid ester. This compound can be obtained by subjecting a compound obtained by addition polymerization of ethylene oxide and / or propylene oxide to decadiene carboxylic acid to an esterification reaction with an alkyl carboxylic acid. Specific examples of the compound represented by the general formula [V] include (polyoxyethylene) ₃₀ -decadienecarboxylic acid ethyl ester. This compound can be obtained by subjecting decadiene carboxylic acid and a compound obtained by addition polymerization of ethylene oxide and / or propylene oxide to ethanol to an esterification reaction. Specific compounds of the compound represented by the general formula [VI], and a bis (polyoxyethylene) ₃₀ of 2-octenyl succinate. This compound is obtained by subjecting 2-octenylsuccinic acid to addition polymerization of ethylene oxide and / or propylene oxide. General formula [VII]
In Specific compounds represented by compounds include bis (polyoxyethylene) ₃₀ of 2-octenyl maleate. This compound is obtained by subjecting 2-octenyl maleic acid to addition polymerization of ethylene oxide and / or propylene oxide. Specific compounds of the compound represented by the general formula [VIII] include:
Examples include itaconic acid (polyoxyethylene) ₃₀ and (polyoxyethylene) ₂₀ diester. This compound is obtained by a diesterification reaction of itaconic acid with poly (ethylene oxide and / or propylene oxide). Also, the formula R ₁ COO (A) _n
Specific examples of the compound represented by R ₂ include (polyoxyethylene) ₂₀ octenyl carboxylate. This compound can be obtained by addition polymerization of octenyl carboxylic acid with ethylene oxide and / or propylene oxide. The amount of the reactive nonionic emulsifiers to be used may be 0.1% by weight or more based on the total amount of monomers, and is not limited as long as various properties of the obtained aqueous dispersion are not reduced. More preferably, the range of 0.1 to 5% by weight is more effective.

The reactive nonionic emulsifiers used as an essential raw material component for preparing the aqueous dispersion of the present invention have been described above.
Combinations with various non-reactive emulsifiers are also possible.

Examples of the emulsifier which may be used in combination include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, other anionic reactive emulsifiers, fluorine surfactants, acrylic oligomers and other substances having surface activity. Of these, nonionic and anionic emulsifiers are preferred because of less formation of aggregates during polymerization.

Typical nonionic emulsifiers include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, ethylene oxide-propylene oxide block copolymer, and the like, while anionic emulsifiers include alkyl (benzene) sulfone. There are alkali metal salts such as acid, alkyl sulfate and polyoxyethylene alkylphenyl sulfate, ammonium salt and amine salt.

Further, instead of or in combination with the above-mentioned anionic emulsifier, a water-soluble oligomer comprising a polycarboxylic acid or a sulfonate can be used. Furthermore, water-soluble polymer substances such as polyvinyl alcohol and hydroxyethyl cellulose can be used as protective colloids. The use amount of the above emulsifiers and the like is preferably 10% by weight or less based on the total amount of monomers, from the viewpoint of physical properties of the obtained coating film.

Next, another essential raw material component,
The fluoroolefin will be described.
If only typical representative examples of the fluoroolefin mentioned here are given, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, 1,1,3,3,3-pentafluoropropylene, 1,1,3,3-tetrafluoropropylene,
1,1,2-trifluoropropylene or 3,3,3
-Including fluoroolefins in a pure sense, such as trifluoropropylene,

Further, chlorotrifluoroethylene,
In a broad sense, the term encompasses those having a halogen atom other than a fluorine atom, such as bromotrifluoroethylene, 1-chloro-1,2-difluoroethylene or 1,1-dichloro-2,2-difluoroethylene. And fluoroolefins.

Of these, the use of hexafluoropropylene, chlorotrifluoroethylene or vinylidene fluoride is particularly desirable from the viewpoint of controlling the reaction during polymerization.

When the fluoroolefin is used in an amount of about 10 to 80% by weight of all the monomers and is introduced into a desired fluororesin, it is particularly satisfactory in weather resistance and the like. You get what you can.

On the other hand, as the other main monomers which can be copolymerized with the fluoroolefin, various types can be considered, and the types and amounts thereof are defined as high weather resistance,
In consideration of various film properties such as chemical resistance, water resistance, alkali resistance, heat resistance and flexibility, it should be appropriately selected and used, and among them, particularly representative ones The following is only an example.

(1) Various unsaturated carboxylic acids, such as crotonic acid, itaconic acid, citraconic anhydride or itaconic anhydride, or various esters thereof; (2) Polymerizable, such as citraconic acid or itaconic acid Various such unsaturated bond-containing polyhydroxyalkyl esters, such as dihydroxyalkyl esters of unsaturated double bond-containing polycarboxylic acids;

(3) Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isoamyl vinyl ether, n-hexyl vinyl ether,
various alkyl vinyl ethers such as n-octyl vinyl ether or 2-ethylhexyl-vinyl ether;

Various cycloalkyl vinyl ethers, such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether; or various aromatic vinyl ethers, such as benzyl vinyl ether or phenethyl vinyl ether;

Various (per) fluoroalkyl vinyl ethers such as perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluorooctyl vinyl ether or perfluorocyclohexyl vinyl ether; or various types such as 4-hydroxybutyl vinyl ether Various vinyl ethers, such as hydroxyalkyl vinyl ethers;

(4) Vinyl acetate, vinyl propionate, n-vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl neononanoate, vinyl neodecanoate, vinyl 2-ethylhexanoate, vinyl laurate or stearin Including acid vinyl, pt-
Various vinyl carboxylate esters, such as vinyl butyl benzoate, vinyl salicylate, vinyl monochloroacetate or vinyl cyclohexanecarboxylate;

(5) Various halogenated olefins such as vinyl chloride or vinylidene chloride; or ethylene, propylene, n-butylene, isobutylene, n-
Various olefins such as pentene; or (6) butadiene, hexadiene, octadiene, decadiene, tetradecadiene, 2-methyloctadiene, decatriene or diallylphthalate,
Various monomers having two or more polymerizable unsaturated double bonds in the molecule; or various hydrolyzable compounds such as vinyltrimethoxysilane, vinyltriethoxysilane or vinyltris (2-methoxyethoxy) silane Various crosslinkable monomers such as silyl group-containing monomers.

Of the various copolymerizable monomers as described above, vinyl ethers and / or vinyl carboxylate, and olefins,
It is suitable to use within a range of 5 to 90% by weight, preferably within a range of 5 to 20% by weight.

Among various copolymerizable monomers, vinyl ethers, when used in an aqueous medium, are easily hydrolyzed depending on the conditions depending on the conditions. It is even more desirable to use other copolymerizable monomers, excluding vinyl ethers.

As the polymerization initiator, those which are generally used in emulsion polymerization can be used.
Although there is no particular limitation, various typical water-soluble inorganic peroxides such as hydrogen peroxide; ammonium persulfate;
Various persulfates, such as potassium or sodium persulfate; various organic peroxides, such as cumene hydroperoxide or benzoyl peroxide;

Various azo initiators, such as azobisisobutyronitrile or azobiscyanovaleric acid (azobisisovaleronitrile), may be used alone or in combination of two or more. Of course.

The amount of the polymerization initiators used is preferably 0.1 to 2% by weight based on the total amount of the monomers. In addition,
Needless to say, a method known as a so-called redox polymerization method using a combination of these polymerization initiators with metal ions and a reducing agent may be used.

In the present invention, the monomers may be used in the presence of water, preferably in the presence of ion-exchanged water, or in the presence of the ion-exchanged water and an emulsifier used as required. , Each as it is, or
In an emulsified state, they are added to the reaction vessel all at once or dividedly, or continuously added dropwise to the reaction vessel, and 0 to 100 in the presence of the polymerization initiators as described above.
C., preferably at a temperature of 30 to 90 ° C. and 3 to 100.
Kg / cm ^2, preferably, it may be Seshimere polymerization Te than in 6~50Kg / cm ² becomes pressure.

In this case, the ratio between the total monomer content and water should be set so that the final solid content is in the range of 20 to 60% by weight. In the emulsion polymerization, a seed polymerization method may be used in which emulsion particles are previously present in an aqueous phase and polymerized in order to grow or control the particle diameter.

The particle size of the aqueous fluororesin dispersion thus obtained is generally from 0.05 to 3 μm (μ
m), while the glass transition temperature (Tg) of the polymers themselves in the aqueous resin dispersion is generally in the range of −20 to + 60 ° C.

The aqueous fluororesin dispersion of the present invention can be mixed with a pigment, a thickener and an organic solvent, if necessary, to form a coating composition.

The amount of the pigments used is desirably 200% by weight or less based on the solid content of the aqueous resin dispersion. If the amount is more than 200% by weight, the resulting coating film is inevitably porous, resulting in poor long-term durability such as water resistance.

As typical examples of the pigments, only typical ones can be mentioned. Titanium oxide, mica, talc,
Various inorganic pigments such as clay, precipitated barium sulfate, silica powder, calcium carbonate, iron oxide, zinc oxide, aluminum powder or carbon; phthalocyanine blue;
Various organic pigments and the like, and further, it is also possible to use so-called dispersed pigments in the form of various pigments as described above dispersed in water with an emulsifier or a dispersant. It is appropriately selected and used according to each purpose.

Next, the organic solvents are added for the purpose of lowering the minimum film forming temperature and further strengthening the film forming state. N-pentane or n
Various saturated hydrocarbons, such as hexane; various aromatic hydrocarbons, such as toluene or xylene; various esters, such as ethyl acetate or butyl acetate;
Various alcohols such as ethyl alcohol, butyl alcohol, 2-ethylhexanol, benzyl alcohol or 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate;

Various ketones such as acetone, methyl ethyl ketone, methyl amyl ketone or methyl isobutyl ketone; various phthalate plasticizers such as dibutyl phthalate or dioctyl phthalate; dimethyl glycol phthalate, dimethyl glycol adipate or dimethyl glycol sebacate Various glycol-based plasticizers;

Various ethylene glycol derivatives such as methyl cellosolve, cellosolve, butyl cellosolve, cellosolve acetate or butyl cellosolve acetate; various diethylene glycol derivatives such as carbitol, carbitol acetate, butyl carbitol or butyl carbitol acetate; Yes, depending on their ability to lower the minimum film forming temperature, they are used in amounts of less than 20% by weight, based on the aqueous dispersion. 20% by weight
The use of an amount exceeding the above range should not be used because there is a possibility that the physical properties of the coating film may be significantly reduced.

Examples of the thickener include the above-mentioned water-soluble oligomers composed of polycarboxylic acids or sulfonates, carboxylic acid-based polymer thickeners, polyvinyl alcohol, methylcellulose, carboxymethylcellulose and hydroxyethylcellulose. Like
Various water-soluble polymer substances, urethane thickeners and the like can be used.

The thickeners may be used in such an amount that the desired viscosity is obtained. However, in consideration of the water resistance of the coating film, 5% by weight or less based on the aqueous dispersion. Is desirable.

Other various additives, for example,
Dispersants, wetting agents, thixotropic agents, ultraviolet absorbers,
The use of antioxidants, water repellents, antifreezes, preservatives / deterrents or defoamers, etc., should be appropriately selected and used while taking into account the performance of the resulting coating film. Good.

Thus, each of the fluororesin aqueous dispersions, which are excellent in various physical properties such as ultra-high weather resistance of the fluororesin, and excellent in long-term storage stability, and which are extremely practical, are also provided. An aqueous coating composition containing the fluororesin aqueous dispersion and pigments as essential components is obtained.

Next, the coating method or means will be described. First, as the base material, concrete skeleton,
Wall materials or roofing materials, including so-called various kinds of alkaline inorganic cured products, as well as general architectural base materials such as metal plates, are not particularly limited, for example, brush coating, roller coating, Various coating means such as spray coating, roll coater coating or showering coating may be appropriately selected according to the situation.

At this time, it is desirable that the composition for construction at a construction site or the like, that is, a so-called room temperature drying type, has a minimum film-forming temperature of 0 ° C. or less.
As a coating method, a known and commonly used method such as brush coating, roller coating or spray coating may be used.

As a condition for drying after the coating, a temperature of 0 ° C. or more, preferably 20 ° C. or more is appropriate. If drying is performed at such a temperature for 7 days, complete drying is possible. It becomes a cured coating film.

On the other hand, the present invention can also be applied to so-called factory line painting of roof materials such as tiles, wall materials, and the like.
According to the respective drying conditions, the minimum film-forming temperature of the aqueous coating composition is generally 60 ° C. or less, preferably 50 ° C. or less. It is preferable to use a known and commonly used method such as roll coating, roller coating, spray coating or showering coating.

Further, the aqueous coating composition may be applied directly on a substrate by one coat or multiple coats, or may be applied by an acrylic or acrylic-styrene copolymer system. An acrylic-urethane combined system, a silicon-acryl combined system, an epoxy-based, a urethane-based, or a silicone-based, generally undercoated with a coating material containing a binder having good alkali resistance, and a top coat formed on the undercoat. The coating composition may be applied to improve and improve the weather resistance of the entire coating system.

In any of the respective coating systems, the dry thick film of the aqueous coating composition is as follows:
5 μm or more is appropriate. When the thickness is less than 5 μm, the long-term durability of the film tends to be insufficient.

[0081]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following, all parts and percentages are by weight unless otherwise specified.

Example 1 In a 2 liter stainless steel autoclave, 720 parts of ion-exchanged water, 16 parts of sodium dodecylbenzenesulfonate, and the following chemical structural formula

[0083]

Embedded image CH ₃ (CH ₂ ) ₇ CH ＝ CH (CH ₂ ) ₇ CO
1 part of polyoxyethylene oleate (hereinafter abbreviated as emulsifier A) represented by O (CH ₂ CH ₂ O) ₂₀ H... [XII] and 3 parts of ammonium hydrogen carbonate The autoclave was dissolved and degassed with nitrogen. 8 parts of crotonic acid, 472 parts of vinyl neononanoate, and 320 parts of liquefied and collected vinylidene fluoride were placed in a pressure-resistant dropping tank, and ethylene was further injected into the autoclave at 15 atm.

The temperature of the autoclave was raised to 80 ° C., and while stirring, a polymerization initiator solution in which 5.6 parts of ammonium persulfate was dissolved in 80 parts of ion-exchanged water, Was added dropwise over 3 hours, and further kept at the same temperature for 3 hours to complete the reaction. The product obtained here has a nonvolatile content of 50% and a pH of 50%.
Was 1.6.

After cooling to room temperature, the pH of the reaction mixture was adjusted to 7.5 with 14% aqueous ammonia, and finally, the non-volatile content was adjusted to 45% with ion-exchanged water. At 0 ° C., the softening point is 70 ° C., and the particle size is 0.09 μm.
m of the aqueous resin dispersion I was obtained.

Examples 2 to 5 and Comparative Examples 1 to 5 Example 1 was repeated except that the monomers and emulsifiers shown in Table 1 were changed to the types and amounts used.
In the same manner as in Examples 2, 3, 4, and 5, respectively.
And aqueous resin dispersions VI, VII, VIII, IX and X of Comparative Examples 1, 2, 3, 4 and 5. The characteristic values of these various aqueous resin dispersions are shown in the same table. Table 2 summarizes the characteristic values of the storage stability.

[0087]

[Table 1]

<< Footnotes to Table 1 >> VF: Abbreviation of "vinylidene fluoride" HFP: Abbreviation of "hexafluoropropylene" CTFE: Abbreviation of "chlorotrifluoroethylene"

<< Footnote to Table 1 >> DBSN: Abbreviation of "sodium dodecylbenzenesulfonate"

<< Footnotes to Table 1 >> The correspondence between the symbols in "reactive nonionic emulsifiers" and the chemical structural formulas is as follows.

A: As described above

B ...

Embedded image

C ...

Embedded image

D ...

Embedded image

[0095]

[Table 2]

[0096]

[Table 3]

[0097]

[Table 4]

[0098]

[Table 5]

<< Footnotes in Table 1 >>

[0100]

Embedded image E: CH ₂ ＣＨCHCH ₂ O (CH ₂ ) ₄ (OCH
₂ CH ₂ ) _n OH (number average molecular weight = about 800)

[0101]

F ... CH ₂ ＝ CHO (CH ₂ ) ₄ (OCH ₂ CH
₂ ) _n OH (number average molecular weight = about 700)

<< Footnotes to Table 1 >> a ... Polyoxyethylene nonylphenyl ether (addition product of 20 mol of ethylene oxide)

B ... polyoxyethylene nonyl phenyl ether (addition product of 30 mol of ethylene oxide)

[0104]

[Table 6]

[0105]

[Table 7]

[0106]

[Table 8]

[0107]

[Table 9]

<< Footnotes in Table 1 >> Storage stability (normal temperature): The sedimentation state of the particles in the aqueous resin dispersion after standing at normal temperature for one year is visually judged.

<< Footnotes in Table 1 >> Storage stability (50 ° C.): The sedimentation state of the particles in the aqueous resin dispersion after standing for 2 months in a constant temperature bath at 50 ° C. is visually judged.

[0110]

[Table 10]

[0111]

As described above, the fluororesin aqueous dispersion of the present invention has extremely high practicality, not only weather resistance, but also can maintain storage stability for a long period of time. In addition, it is also characterized by stain resistance.
By using such a highly practical aqueous fluororesin dispersion of the present invention, it is possible to obtain an aqueous coating composition having excellent long-term storage stability, and also having excellent ultra-high weather resistance and stain resistance. I can do it.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-170402 (JP, A) JP-A-4-272903 (JP, A) JP-A-5-39328 (JP, A) 32102 (JP, A) JP-A-55-73747 (JP, A) JP-A-62-104803 (JP, A) JP-A-61-261367 (JP, A) (58) Fields investigated (Int. ⁷ , DB name) C08L 27/12-27/20 C08F 214/18-214/28 C09D 127/12-127/20 C09D 5/02

Claims (5)

(57) [Claims] 1. A compound of the general formula Wherein R ₁ and R ₂ are either one of
Is a hydrocarbon having at least one polymerizable unsaturated bond
A hydrocarbon group having 6 to 24 carbon atoms.
Shall represent the original, R ₃ is assumed to represent an alkyl group or a proton carbon atoms comprising 1 to 4, A is assumed to represent a ethylene oxide bonds and / or propylene oxide bond, m is 1 or 2 becomes an integer And n is an integer of 5 or more. ] [However, R ₁ in the formula is intended to represent a saturated hydrocarbon group or unsaturated carbon atoms becomes 6 to 24, R ₂
Has two carbon atoms when R ₁ is a saturated hydrocarbon
And R 4 represents an alkyl group having 1 to 4 carbon atoms, and A represents an ethylene oxide bond and / or a propylene oxide bond when R ₁ is an unsaturated hydrocarbon. M is an integer of 1 or 2, and n
Is an integer of 5 or more. ] Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ represents an alkyl group having 1 to 4 carbon atoms or A represents a proton, A represents an ethylene oxide bond and / or a propylene oxide bond, m is an integer of 1 or 2, and n is an integer of 5 or more. ] Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, R ₂ represents a proton or a methyl group, ₃ represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond,
Further, n is an integer of 5 or more. ] Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, R ₂ represents a proton or a methyl group, ₃ represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond,
Further, n is an integer of 5 or more. ] Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ and R ₃ are the same, Represents an alkyl group having 1 to 4 carbon atoms or a proton, and A and B may be the same or different,
M and n may be the same or different, and at least one of them is an integer of 5 or more, and the other is 0. Alternatively, it is an integer of 1 or more. ] Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ and R ₃ are the same, Represents an alkyl group having 1 to 4 carbon atoms or a proton, and A and B may be the same or different,
M and n may be the same or different, and m and n may be the same or different, and at least one of them is an integer of 5 or more, and the other is It is assumed to be 0 or an integer of 1 or more. Embedded image Wherein R ₁ and R ₂ each represent an alkyl group having 6 to 24 carbon atoms or a proton, which may be the same or different, and at least one of them is an alkyl group A and B each represent an ethylene oxide bond and / or a propylene oxide bond, which may be the same or different, and m and n are
Although each may be the same or different, at least one of them is an integer of 5 or more,
The other is an integer of 0 or 1 or more, and r is an integer of 1 to 4. ] Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ represents an alkyl group having 1 to 4 carbon atoms or A represents a proton, A represents an ethylene oxide bond and / or a propylene oxide bond, and n is an integer of 5 or more. ] A fluororesin aqueous dispersion obtained by copolymerizing at least one compound selected from the group consisting of compounds represented by the formula (1) and a fluoroolefin as essential raw material components. 2. A compound of the general formula Wherein R ₁ and R ₂ are either one of
Is a hydrocarbon having at least one polymerizable unsaturated bond
A hydrocarbon group having 6 to 24 carbon atoms.
Shall represent the original, R ₃ is assumed to represent an alkyl group or a proton carbon atoms comprising 1 to 4, A is assumed to represent a ethylene oxide bonds and / or propylene oxide bond, m is 1 or 2 becomes an integer And n is an integer of 5 or more. [Image Omitted] [However, R ₁ in the formula is intended to represent a saturated hydrocarbon group or unsaturated carbon atoms becomes 6 to 24, R ₂
, When R ₁ is a saturated hydrocarbon group, a represents an alkenyl group having a carbon number becomes 2-4, when R ₁ is an unsaturated hydrocarbon group, is from 1 to 4 carbon atoms A represents an alkyl group, A represents an ethylene oxide bond and / or a propylene oxide bond, m is an integer of 1 or 2, and n is an integer of 5 or more. ] Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ represents an alkyl group having 1 to 4 carbon atoms or A represents a proton, A represents an ethylene oxide bond and / or a propylene oxide bond, m is an integer of 1 or 2, and n is an integer of 5 or more. ] Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, R ₂ represents a proton or a methyl group, ₃ represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond,
Further, n is an integer of 5 or more. ] Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, R ₂ represents a proton or a methyl group, ₃ represents an alkyl group having 1 to 4 carbon atoms, A represents an ethylene oxide bond and / or a propylene oxide bond,
Further, n is an integer of 5 or more. ] Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ and R ₃ are the same, Represents an alkyl group having 1 to 4 carbon atoms or a proton, and A and B may be the same or different,
M and n may be the same or different, and at least one of them is an integer of 5 or more, and the other is 0. Alternatively, it is an integer of 1 or more. ] Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ and R ₃ are the same, Represents an alkyl group having 1 to 4 carbon atoms or a proton, and A and B may be the same or different,
M and n may be the same or different, and m and n may be the same or different, and at least one of them is an integer of 5 or more, and the other is It is assumed to be 0 or an integer of 1 or more. Embedded image Wherein R ₁ and R ₂ each represent an alkyl group having 6 to 24 carbon atoms or a proton, which may be the same or different, and at least one of them is an alkyl group A and B each represent an ethylene oxide bond and / or a propylene oxide bond, which may be the same or different, and m and n are
Although each may be the same or different, at least one of them is an integer of 5 or more,
The other is an integer of 0 or 1 or more, and r is an integer of 1 to 4. [Image Omitted] Wherein R ₁ represents a hydrocarbon group having at least one polymerizable unsaturated bond and having 6 to 24 carbon atoms, and R ₂ represents an alkyl group having 1 to 4 carbon atoms or A represents a proton, A represents an ethylene oxide bond and / or a propylene oxide bond, and n is an integer of 5 or more. A fluororesin aqueous solution obtained by copolymerizing at least one compound selected from the group consisting of compounds represented by the following, a fluoroolefin, and other copolymerizable monomers as essential raw material components: Dispersion. 3. An aqueous coating composition obtained by mixing a pigment with the aqueous fluororesin dispersion according to claim 1. 4. An aqueous coating composition obtained by mixing a pigment and a thickener with the fluororesin aqueous dispersion according to claim 1 or 2. 5. An aqueous coating composition obtained by mixing a pigment, a thickener, and an organic solvent with the fluororesin aqueous dispersion according to claim 1 or 2.